Luminescent Properties of A Novel Terbium Complex Tb(o-BBA)_3(phen)

A novel rare earth complex of terbium ion with 2-benzoylbenzoic acid and 1, 10-phenathroline （Tb（o-BBA）3 （phen）, o-BBA-2-benzoylbenzoic acid, phen = 1, 10-phenathroline） was used as an electroluminescent material for the first time. The Tb complex was blended with poly（N-vinylcarbazole） （PVK） in different weight ratios and spinn to coated into films （noted as PVK ：Tb films）. The photoluminescence （PL） properties of films were investigated and the optimum weight ratio between PVK and Tb（o-BBA）3（phen） was found to be 3：1. Monolayer devices with the structure ITO/PVK： Tb/AI were fabricated and emitted green light, which was characteristic of Tb^3＋ emission. The results show that mecha- nisms for PL and EL are different. The PL is considered to be caused because of energy transfer and direct excitation to the Tb（o-BBA）3（phen） molecule, while EL is mainly on charging trapping.

Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).

Intercalation Assembly, Characterization and Luminescent Properties of Novel Supramolecular Composite Materials, Tb(Ⅲ) Complex with Tetrapodal Ligand-Montmorillonite

Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.

Synthesis of Eu(Ⅲ) and Tb(Ⅲ) Complexes with New Aryl Amide Type Tetrapodal Ligand and Their Luminescence Properties

A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.

Synthesis and properties of Tb^(3+) isomultiligand complexes

Four kinds of terbium containing monomers were synthesized by the reaction of Tb isoproxides with acrylic acid and β diketones. The composition and structure of these monomers were confirmed by FT IR, UV spectroscopy and elemental analysis. DTA and TG analyses reveal that the decomposition temperature of these monomers is in the range of 190～200 ℃. The fluorescence properties of these monomers were studied. Under the excitation of UV light, these monomers exhibit characteristic luminescence of terbium ion, the fluorescent intensity is affected by the polarity of solvent and triplet state of ligand. In solid state, the monochromatic index of luminescence is enhanced.

Synthesis and fluorescence properties of Tb(Ⅲ) complexes with pyridine-2,6-dicarboxylic acid derivatives

Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.

Determination of alkali-labile phosphoprotein phosphorus from fish plasma using the Tb^(3+)-tiron complex as a fluorescence probe

A sensitive method based on the fluorescence quenching effect of the Tb^3＋-Tiron complex is proposed for the determination of alkali-labile phosphoprotein phosphorus （ALP） released from fish plasma. The detection limit was 5.4 ng/ml （S/N=2）, and the relative standard deviation of the quenching effect （6 replicates） was 4.6%. The results obtained by the proposed method were in good agreement with those obtained by the colorimetric assay. The advantages of the present method are its relatively simple detection procedure, the lack of toxic organic solvents, and high sensitivity.

Syntheses and Magnetism of Binuclear Tb(Ⅲ)-Tb(Ⅲ)Complexes with Dianion of Chloranilic Acid as Bridging Ligand

The syntheses, spec(?) complexes are of significance for understanding mechanisms of magnetic interaction between metal ions and the exploitation of the synthesis of molecular magnetic materials. There were a few works reported previously on the syntheses and magnetic in-

Fluorescence of Tb-Ibuprofenum-Phen Complex and New Tissue Staining Method

A new complex Tb(IB)_3(phen)·2H_2O that gives off green fluorescence was synthesized. The results show that the strong fluorescence emitting of 490 and 545 nm for Tb 3+ in the Tb(IB)_3(phen)·2H_2O complex is related to the transitions 5D_4-7F_6 and 5D_4-7F_5, respectively. The results indicate that the complex is concentrated on the nuclei regions in the section of onion toot tip tissues and the nuclei are high lighted under fluorescent microscope. It is possible that the Tb(IB)_3(phen)·2H_2O complex can be developed as a fluorescent dye in biological and pathological studies.

铽配合物Tb(o-BBA)_3(phen)有机电致发光研究

合成了一种新的稀土配合物邻苯甲酰苯甲酸-1,10-菲罗啉-铽(Tb(o-BBA)3(phen))并用于有机电致发光。研究了Tb(o-BBA)3(phen)与PVK混合薄膜的光致发光特性,找出了PVK∶Tb的最佳比例为3∶1。制备了结构为ITO/PVK∶Tb/Al的单层电致发光器件,得到了铽离子的特征光谱,其电流-电压特性(I-V)在一定电压范围内符合空间电荷限制电流机制。研究结果表明稀土铽配合物Tb(o-BBA)3(phen)掺杂PVK体系的光致发光是源于PVK到Tb配合物的能量传递及稀土Tb配合物的直接激发两种作用机制,而电致发光以载流子俘获为主。

不同有机酸配体对Tb(Ⅲ)离子荧光效率的影响

对合成的七种Tb-配合物的荧光发射光谱和激发光谱进行了比较研究,重点比较了七种Tb-配合物的荧光强度,并从配体结构、能量传递和能级匹配等方面分析了不同配体对Tb(Ⅲ)离子荧光效率的影响,同时讨论了七种Tb-配合物的红外光谱和拉曼光谱。研究表明,配体不影响Tb(Ⅲ)离子的特征发射峰位置,只影响其荧光效率。配体的共轭性、刚性越好,配合物荧光效率越高,二元酸比一元酸更有利于增强Tb(Ⅲ)离子的荧光效率。

Eu^(3+),Tb^(3+)混配配合物的激光诱导荧光

利用激光诱导荧光技术研究了两种三价稀土金属离子（EU3＋，Tb3＋）的μ－二酮与有机配体混配络合物中金属离子的寿命及其能级结构，得到了Eu3＋的能级常数．

Tb-N-苯基邻氨基苯甲酸-1,10-菲咯啉二元、三元配合物的合成、表征及荧光性能

合成了稀土Tb -N 苯基邻氨基苯甲酸 -1,10 - 菲咯啉二元、三元配合物。通过元素分析确定二元配合物的组成为TbL3 ·4H2 O ,三元配合物的组成为TbL3 phen·2H2 O(L :N 苯基邻氨基苯甲酸根 ,phen :1,10- 菲咯啉 ) ,讨论了两种配合物的谱学性质。通过荧光光谱测试发现 ,形成的TbL3 ·4H2 O二元配合物的荧光强度明显降低 ,1,10 - 菲咯啉作为第二配体引入后 ,使Tb3 + 的发光强度继续降低 ,这说明了Tb3 + 的发光强度与配体的结构有关 ,通过结构、能量传递和能量匹配对此做了进一步的解释。

2,5-二羟基对苯二甲酸Tb(Ⅲ)配位聚合物的合成与表征

采用溶剂热法合成了一个配位聚合物{[Ln2(H2-DHBDC)3(H2O)4](H2O)2}n(H2-DHBDC=2,5-二羟基对苯二甲酸)。利用X-射线单晶衍射(SCXRD)、元素分析(EA)、红外光谱(FTIR)、热重分析(TG)和荧光分光光度法(FS)等对其结构和性质进行了分析与表征。结果表明:晶体属于单斜晶系,P-1空间群,晶胞参数a=1.0640(8)nm,b=1.1239(9)nm,c=1.5232(12)nm,α=99.351(11)°,β=99.511(11)°,γ=92.482(12)°,V=1768(2)nm3,Z=2。八个氧原子在铽离子周围形成一个变形的三角十二面体配位环境,金属离子通过与配体连接形成具有一定孔道的三维结构。荧光分析测试表明,配合物具有较好的荧光性。

核苷酸、聚核苷酸和核酸猝灭Tb^(3+)-钛铁试剂络合物荧光的机理研究

研究了核苷酸、聚核苷酸和核酸对Tb3+－钛铁试剂（TR）络合物的荧光碎灭机理，认为荧光猝灭过程是核苷酸、聚核苷酸和核酸分子中的磷酸基组分与TR竞争Tb3+离子，生成实验条件下无荧光的二元络合物的静态猝灭过程；用Tb3+－TR络合物荧光探针研究DNA嵌入剂和金属离子与DNA相互作用的实验结果说明这一机理是合理的．

微波辅助合成色控型CMC-Tb/Eu纳米复合物的荧光性质

微波辅助下通过共同沉淀法制备了一系列可色控的CMC-Tb/Eu复合物,并通过SEM-EDS、TEM、XPS、UV-Vis,荧光光谱和荧光寿命检测等方法考察了复合物的形貌、结构、荧光性能以及能量转移特征.结果表明:CMC-Tb/Eu复合物的表面与CMC的相比裂痕多,有小粒子集聚于CMC表面,颗粒为实心结构,平均直径为75~98 nm;纳米复合物中金属离子都与CMC分子链上的—OH、—COO^-以及—COC—中O原子发生配位键合和离子;CMC为主要的光能量吸收体,在其与稀土离子的能量传递过程中,传递给Tb^(3+)的效率要远大于传递给Eu^(3+);在激发光为350 nm下,CMCTb/Eu发射光谱中存在~5D_4→~7F_5(544 nm)和~5D_4→~7F_6(489 nm)Tb^(3+)跃迁峰;589 nm和616 nm附近的两个发射峰是由Tb^(3+)的~5D_4→~7F_3和~5D_4→~7F_4跃迁以及Eu^(3+)的~5D_0→~7F_1和~5D_0→~7F_2跃迁叠加所致;实现了荧光光色可控.Tb^(3+)的~5D_4→~7F_5跃迁峰强度变化以及纳米复合物的荧光寿命变化证明了纳米复合物存在Tb(Ⅲ)Eu(Ⅲ)能量转移.

芳羧酸功能化的聚苯乙烯与Tb(Ⅲ)离子形成的高分子-稀土配合物的荧光发射性能

通过大分子反应将苯甲酸(BA)键合在聚苯乙烯(PS)侧链,制得芳羧酸功能化的聚苯乙烯PSBA。以PSBA为大分子配基,以邻菲啰啉(Phen)为小分子配体,与Tb(Ⅲ)离子配位,分别制备了二元配合物PS-(BA)3-Tb(Ⅲ)与三元配合物PS-(BA)1-Tb(Ⅲ)-(Phen)2及PS-(BA)1-Tb(Ⅲ)-(Phen)3,采用红外光谱(FTIR)和紫外吸收光谱(UV)对配合物进行了表征,深入研究了配合物(溶液与薄膜)的荧光发射性能。研究结果表明,大分子配基PSBA与Tb(Ⅲ)离子所形成的二元或三元高分子-稀土配合物均能发射出很强的Tb(Ⅲ)离子特征荧光,即键合在PSBA侧链的配基BA能有效地敏化Tb(Ⅲ)离子的荧光发射。与二元配合物相比较,以小分子Phen为第二配体所形成的两种三元配合物具有强度更高的荧光发射。

Tb(N-PA)_3(TPPO)_2配合物的合成及荧光性能

合成了铽、N-苯基邻氨基苯甲酸(N-HPA)和三苯基氧化膦(TPPO)的稀土配合物,采用元素分析、紫外光谱、红外光谱初步进行了结构表征,研究了配合物Tb(N-PA)_3(TPPO)_2的荧光性能.结果表明,铽、N-苯基邻氨基苯甲酸引入第二配体三苯基氧化膦后,敏化了铽离子的发光,配合物的发光强度显著增加,Tb(N-PA)_3(TPPO)_2三元配合物有较好的荧光性.

吡啶-2,6-二甲酰胺衍生物Tb(Ⅲ)、Eu(Ⅲ)配合物的制备及荧光性能测试

从吡啶-2，6-二甲酸（L1）出发，合成了2种含有多个共轭体系和多齿的N^2，N^6-二（3-甲基吡啶）-2-取代吡啶-2，6-二甲酰胺（L2）配体和N^2，N^6-二对甲苯基吡啶-2，6-二甲酰胺（L2）配体；制备了化合物N^2，N^6-二（3-甲基吡啶）-2-取代吡啶-2，6-二甲酰胺（L2）与Tb（Ⅲ）和Eu（Ⅲ）的配合物，培养出了单晶。通过红外光谱、元素分析和X射线单晶衍射仪确定配合物的组成和结构。结果表明：在Tb（Ⅲ）配合物的稀溶液中，当溶液pH值为7时荧光强度最强，pH值大于或小于7荧光强度都逐渐减弱；当溶液pH为7时，N^2，N^6-二（3-甲基吡啶）-2-取代吡啶-2，6-二甲酰胺对Tb（Ⅲ）的荧光强度敏化远大于吡啶-2，6-二甲酸；N^2,N6-二（3-甲基吡啶）-2-取代吡啶-2，6-二甲酰胺和吡啶-2，6-二甲酸与Eu（Ⅲ）形成稀的配合物溶液的荧光强度随pH值的增加而增大（pH3～11）。

新型Tb(Ⅲ)配合物及与牛血清蛋白(BSA)结合的研究

合成了一个新型配体,2-甲基-6-(8-喹啉基)-吡啶二甲酸酯(L),并制备和表征了其的Tb(III)配合物,Na4Tb(L)2Cl4·3H2O。荧光光谱显示配体L是一个有效的敏化稀土离子发光的配体。Stern-Volmer分析显示荧光猝灭机制为静态猝灭。结合常数研究证明其只有一个结合位点。